JPH026590A - Production of phosphor - Google Patents
Production of phosphorInfo
- Publication number
- JPH026590A JPH026590A JP15489788A JP15489788A JPH026590A JP H026590 A JPH026590 A JP H026590A JP 15489788 A JP15489788 A JP 15489788A JP 15489788 A JP15489788 A JP 15489788A JP H026590 A JPH026590 A JP H026590A
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- mol
- rare earth
- boron
- compounds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 4
- 150000001805 chlorine compounds Chemical class 0.000 claims abstract description 4
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 4
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- 150000001639 boron compounds Chemical class 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 150000002222 fluorine compounds Chemical class 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 229920001021 polysulfide Polymers 0.000 claims description 2
- 239000005077 polysulfide Substances 0.000 claims description 2
- 150000008117 polysulfides Polymers 0.000 claims description 2
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 2
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 20
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 12
- 229910052796 boron Inorganic materials 0.000 abstract description 10
- UAHZTKVCYHJBJQ-UHFFFAOYSA-N [P].S=O Chemical compound [P].S=O UAHZTKVCYHJBJQ-UHFFFAOYSA-N 0.000 abstract description 6
- 150000002910 rare earth metals Chemical class 0.000 abstract description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910019142 PO4 Inorganic materials 0.000 abstract description 2
- 229910052771 Terbium Inorganic materials 0.000 abstract description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 abstract description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 229910017673 NH4PF6 Inorganic materials 0.000 abstract 1
- 229910002651 NO3 Inorganic materials 0.000 abstract 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract 1
- 229910000421 cerium(III) oxide Inorganic materials 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 235000021317 phosphate Nutrition 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- -1 rare earth oxysulfide Chemical class 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 229910013184 LiBO Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000001513 hot isostatic pressing Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001477 LaPO4 Inorganic materials 0.000 description 1
- 229910003252 NaBO2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium nitrate Inorganic materials [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910001940 europium oxide Inorganic materials 0.000 description 1
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910001938 gadolinium oxide Inorganic materials 0.000 description 1
- 229940075613 gadolinium oxide Drugs 0.000 description 1
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910003451 terbium oxide Inorganic materials 0.000 description 1
- SCRZPWWVSXWCMC-UHFFFAOYSA-N terbium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tb+3].[Tb+3] SCRZPWWVSXWCMC-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Conversion Of X-Rays Into Visible Images (AREA)
- Measurement Of Radiation (AREA)
- Luminescent Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、例えばＸ線用シンチレータとして優れた特性
を示す、透明度の高い希土類オキシサルファイドセラミ
ックスを得るために好適な大粒径の希土類オキシサルフ
ァイド系の螢光体の製造方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention is directed to a large particle diameter rare earth oxysulfide ceramic suitable for obtaining highly transparent rare earth oxysulfide ceramics that exhibit excellent properties as, for example, an X-ray scintillator. The present invention relates to a method for producing a type of phosphor.
希土類オキシサルファイド系の螢光体については、米国
特許第３４１８２４６号に付活剤で活性化した該螢光体
が開示されている。また、米国特許第３５０２５９０号
に、該螢光体の実用的な製造方法についての記載がある
。後者の製造方法は、酸化ガドリニウム（ａｄｚｏａ）
−酸化ランタン（Ｌａｉｏｉ）および酸化イツトリウム
（ｙ ｚ○３）の中から選ばれる少なくとも１種の酸化
物と、付活剤としての希土類酸化物および加熱によって
硫化アルカリおよびポリ硫化アルカリを生ずる組成物と
からなる混合物を７００〜１２５０℃で加熱する工程と
、次いでその加熱生成物を冷却する工程とからなる方法
で、上記工程を経て得られた試料を水洗して水溶性物質
（硫化アルカリ）を除去することによって、平均粒径１
〜８μｍの希土類オキシサルファイド螢光体が得られて
いる。Regarding rare earth oxysulfide-based phosphors, US Pat. No. 3,418,246 discloses the phosphors activated with an activator. Further, US Pat. No. 3,502,590 describes a practical method for manufacturing the phosphor. The latter manufacturing method uses gadolinium oxide (adzoa)
- at least one oxide selected from lanthanum oxide (Laioi) and yztrium oxide (yz○3), a rare earth oxide as an activator, and a composition that generates alkali sulfide and polyalkali sulfide upon heating; A method consisting of a step of heating a mixture consisting of 700 to 1250 ° C., and then a step of cooling the heated product, and washing the sample obtained through the above steps with water to remove water-soluble substances (alkali sulfide). By doing this, the average particle size 1
~8 μm rare earth oxysulfide phosphors have been obtained.
また、上記製造方法の改良として、希土類酸化物の一部
を希土類リン酸塩で置換する方法が特開昭第５５−１５
７６７８号に開示されている。In addition, as an improvement to the above manufacturing method, a method of substituting a part of the rare earth oxide with a rare earth phosphate was published in Japanese Patent Application Laid-open No. 55-15.
No. 7678.
〔発明が解決しようとする課題〕
Ｘ線用シンチレータとして優れた特性を示す希土類オキ
シサルファイドセラミックスについて、透明度の高い高
効率の該セラミックスを得るためには、その原材料とな
る希土類オキシサルファイド螢光体ができるだけ大粒径
であることが望ましいが、上記従来技術の方法によって
得られる螢光体は平均粒径が高々１０μｍに止まってい
た。[Problem to be solved by the invention] Regarding rare earth oxysulfide ceramics that exhibit excellent properties as an X-ray scintillator, in order to obtain highly transparent and highly efficient ceramics, it is necessary to Although it is desirable to have as large a particle size as possible, the average particle size of the phosphor obtained by the above-mentioned prior art method was no more than 10 μm.
本発明の目的は、平均粒径が少なくとも２０μｍ以上の
希土類オキシサルファイド螢光体を得ることのできる製
造方法を提供することにある。An object of the present invention is to provide a manufacturing method capable of obtaining a rare earth oxysulfide phosphor having an average particle size of at least 20 μm or more.
上記目的は、−数式（Ｌｎ、−ｘ Ｍｘ ）ｘ Ｏａ
（但し、ＬｎはＹ、Ｌａ、Ｇｄの中から選ばれる少なく
とも１種の元素、ＭはＰｒ、Ｅｕ、Ｔｂの中から選ばれ
る少なくとも１種の元素、Ｘは０．００００１〜０．１
の範囲の値）で表わされる酸化物、ＬｎおよびＭのリン
酸塩化合物、加熱分解によってＣｅ２ｏ３を生ずるＣｅ
化合物、加熱により硫化アルカリおよびポリ硫化アルカ
リを生ずる組成物、ホウ素化合物およびフッ素化合物か
らなる混合物を９００〜１４００℃の温度で加熱焼成す
る工程と、次いで、該焼成生成物を冷却した後水洗する
工程とからなる製造方法を適用することによって達成す
ることができる。The above purpose is - Formula (Ln, -x Mx ) x Oa
(However, Ln is at least one element selected from Y, La, and Gd, M is at least one element selected from Pr, Eu, and Tb, and X is 0.00001 to 0.1
), phosphate compounds of Ln and M, Ce2o3 which is produced by thermal decomposition
A step of heating and baking a mixture consisting of a compound, a composition that produces an alkali sulfide and alkali polysulfide when heated, a boron compound and a fluorine compound at a temperature of 900 to 1400°C, and then a step of cooling the baked product and washing it with water. This can be achieved by applying a manufacturing method consisting of.
本発明方法のもっとも特徴とするところは、希土類オキ
シサルファイド螢光体の製造方法において、従来技術に
おける材料組成に加えて、さらに、ホウ素化合物を用い
たことにある。ここで、該ホウ素化合物としては、Ｈ，
ＢＯ，、Ｂ、Ｏ，、Ｌｉ。The most distinctive feature of the method of the present invention is that, in addition to the material composition used in the prior art, a boron compound is used in the method for producing a rare earth oxysulfide phosphor. Here, the boron compound includes H,
BO,,B,O,,Li.
Ｂ４０ｔ、Ｎａ、Ｂ、Ｏ，、ｘ ＊ Ｂ２Ｏｔ、Ｋ、Ｂ
、Ｏ，、ＮａＢＯ，およびＬｉＢＯ，の中から選ばれる
少なくとも１種のホウ素化合物を用いることが望ましく
、平均粒径２０μｍ以上の希土類オキシサルファイド螢
光体を得るための該ホウ素化合物の量は、ホウ素原子に
換算して、希土類元素１グラム原子当り０．０２〜０．
４グラム原子の範囲が適当である。０．４グラム原子よ
りも多量に添加した場合には得られる螢光体粒子径はさ
らに大きくなるが、螢光体中に非発光物質が混入してく
るので好ましくない、なお、ホウ素化合物としては、上
記した化合物以外に、加熱によってホウ素化合物を生ず
るような混合物成分を用いてもよい６
フッ素化合物あるいは塩素化合物およびＣｅ化合物を添
加した理由は特公昭第６０−４８５６号に開示されてい
るので割愛する。B40t, Na, B, O,, x * B2Ot, K, B
It is desirable to use at least one boron compound selected from , O, , NaBO, and LiBO, and the amount of the boron compound to obtain a rare earth oxysulfide phosphor having an average particle size of 20 μm or more is In terms of atoms, 0.02 to 0.0.
A range of 4 gram atoms is suitable. If it is added in an amount larger than 0.4 gram atoms, the resulting phosphor particle size will become even larger, but this is not preferable because non-luminescent substances will be mixed into the phosphor. In addition to the above-mentioned compounds, mixture components that produce boron compounds when heated may also be used.6 The reasons for adding fluorine compounds or chlorine compounds and Ce compounds are disclosed in Japanese Patent Publication No. 60-4856, so we omit the explanation here. do.
また、付活剤としての希土類酸化物としては、酸化プラ
セオジム、酸化テルビウムおよび酸化ユーロピウムの中
から選ばれる少なくとも１種の酸化物を用いることが望
ましいが、他の希土類酸化物を用いてもよい。Further, as the rare earth oxide as the activator, it is desirable to use at least one oxide selected from praseodymium oxide, terbium oxide, and europium oxide, but other rare earth oxides may be used.
上述の製造方法を用いて作成した平均粒径３８μｍのＧ
ｄ、Ｏ，Ｓ ： Ｐｒ螢光体を用いてＸＱＣＴ用固体検
出器を作成して、その特性を調べた。すなわち、まず、
上記Ｇｄ、Ｏ，Ｓ ： Ｐｒ螢光体に焼結助剤として０
．１重量パーセントのＬｉ、ＧｅＦ、を加えて混合し、
これを鉄製のカプセルに詰め、真空封止した後、 １３
００℃、１０００気圧、３時間の条件で熱間静水圧加圧
成形（Ｈｏｔ ｌ５ｏｓｔａｔｉｃ Ｐｒｅｓｓｉｎｇ
、 ＨＩＦ）を行った０次いで、鉄容器を除去して焼結
成形体を取り出し、厚さ１．２ｆｆｌに加工した後、シ
リコンホトダイオードと組合わせて固体検出器を作製し
た。この検出器にＸ線（管電圧ｔｚｏｋｖ、電流２００
ｍＡ）を照射した場合の発光出力は、従来の製造方法で
作成した平均粒径５μｍの同一組成の螢光体を用いて上
記と同様の方法で作製した固体検出器の発光出力と比べ
、約１．７倍の値を示した。G with an average particle size of 38 μm produced using the above manufacturing method
A solid-state detector for XQCT was created using a d, O, S: Pr phosphor, and its characteristics were investigated. That is, first,
The above Gd, O, S: 0 as a sintering aid in the Pr phosphor
．． Add and mix 1 weight percent Li, GeF,
After filling this into an iron capsule and vacuum sealing it, 13
Hot isostatic pressing at 00°C, 1000 atm, and 3 hours.
Then, the iron container was removed, the sintered compact was taken out, processed to a thickness of 1.2 ffl, and combined with a silicon photodiode to fabricate a solid-state detector. X-rays (tube voltage tzokv, current 200
The luminescence output when irradiated with 5 mA) is approximately 100% compared to the luminescence output of a solid-state detector manufactured in the same manner as above using a phosphor of the same composition with an average particle size of 5 μm manufactured by a conventional manufacturing method. The value was 1.7 times higher.
ここで、平均粒径３８μｍの螢光体を用いて作製した固
体検出器の方が発光出力が高い値を示すのは、焼結体に
おける粒界が少なく、光の散乱や吸収が少なくなるため
と思われる。この焼結体シンチレータはＸ線ＣＴ用とし
て極めて有用である。Here, the solid-state detector made using a phosphor with an average particle size of 38 μm exhibits a higher luminescence output value because there are fewer grain boundaries in the sintered body, which reduces light scattering and absorption. I think that the. This sintered scintillator is extremely useful for X-ray CT.
以下、本発明の螢光体の製造方法について、実施例によ
って具体的に説明する。Hereinafter, the method for manufacturing a phosphor of the present invention will be specifically explained with reference to Examples.
実施例 １〜８
まず、下記材料をビーカーに秤量採取し、これに水を加
えて十分混合した後乾燥する。Examples 1 to 8 First, the following materials were weighed and collected in a beaker, water was added thereto, the mixture was thoroughly mixed, and then dried.
Ｇ ｄ、 ０ 、 ０．９１９１モル
ＧｄＰＯ４０，１５９８モル
Ｐｒ、 Ｏ，、０，０００３３モル
Ｇｏ（Ｎ Ｏ，）、 ・６ Ｈ２Ｏ０，０ＯＯＯＬ２モ
ル次いで、上記混合物をアクリル製のびんに入れ。G d, 0, 0.9191 mol GdPO 40,1598 mol Pr, O,, 0,00033 mol Go (N O,), .6 H2O 0,0 OOOL 2 mol Next, the above mixture was placed in an acrylic bottle.
さらに下記材料を加え、びんを回転して内容物を良く混
合させる。Add the following ingredients and rotate the bottle to mix the contents well.
８ ３．２９モルＮａ、 Ｃ０
，０，４５２モル
ＬＬ、Ｃ０，０，４５２モル
に、 Ｐ Ｏ４０，１２１モ／ｌ／
Ｎ Ｈ，Ｐ Ｆ、 ０．０３０モルホ
ウ素化合物 希土類元素１グラ（第１表第２
欄） ム原子当り０．１２グラム原子のホウ素
を含む量
この混合材料をアルミするつぼに詰め、アルミナのふた
をした後、空気中１２５０℃で６時間焼成する。8 3.29 mol Na, C0
, 0,452 mol LL, C 0,0,452 mol, P O 40,121 mol/l/NH, PF, 0.030 mol boron compound 1 gram of rare earth element (Table 1, 2
Column) Amount containing 0.12 g atom of boron per atomic atom This mixed material is packed in an aluminum crucible, covered with an alumina lid, and then calcined in air at 1250° C. for 6 hours.
焼成物をるつぼから取り出し、純水を加えてスタージー
で攪拌する。このとき、Ｎ ａ ２ Ｓ ｘが純水に溶
出するため溶液が黄色となるが、これが無色となるまで
水洗を繰り返す１次いで、０．１５規定のＨ（１１で処
理した後、再び水洗し、得られた螢光体を１４０℃で乾
燥する。Remove the fired product from the crucible, add pure water, and stir with a stargie. At this time, the solution becomes yellow because the Na 2 S The obtained phosphor is dried at 140°C.
このようにして得られた螢光体はいずれも（Ｇｄｏ ５
ｓｓＰｒｏ ｌｌｌｌｌｃｅｍ ｔｏ−ｂ）ｚｏｚｓ
： （Ｆ）の組成からなるものであり、その平均粒径（
顕微鏡写真から求めた）を、添加したホウ素化合物の種
類とともに、第１表に示した。なお、表中で、Ｌｎは配
合したすべての希土類元素を示すものである。All of the phosphors obtained in this way (Gdo 5
ssPro llllllcem to-b) zozs
: It consists of the composition of (F), and its average particle size (
(determined from micrographs) are shown in Table 1 along with the type of boron compound added. In addition, in the table, Ln indicates all the rare earth elements blended.
表の結果かられかるように、螢光体製造の材料成分とし
てホウ素化合物を加えることによって。As can be seen from the results in the table, by adding boron compounds as material components for phosphor production.
添加しないものに比べて、非常に大きな平均粒径を有す
る螢光体を得ることができる。It is possible to obtain a phosphor having a much larger average particle size than that without the addition.
第 １ 表
実施例 ９
下記材料をビーカーに秤量採取し、これに水を加えて十
分混合した後乾燥する。Table 1 Example 9 The following materials were weighed into a beaker, water was added thereto, mixed thoroughly, and then dried.
Ｌａｔｏ、 ０．９１９１モルＬａ
Ｐ ０． ０．１５９８モルＰｒ、０
１□０．０００３３モル
Ｃ６（Ｎ ０３）３ ・６ Ｈｚ ＯＯ，００００１２
モ）ｔ／次いで、上記混合物をアクリル製のびんに入れ
、さらに下記材料を加え、びんを回転して内容物を良く
混合させる。Lato, 0.9191 mol La
P0. 0.1598 mol Pr, 0
1□0.00033 mol C6(N 03)3 ・6 Hz OO,000012
M) Next, put the above mixture into an acrylic bottle, add the following materials, and rotate the bottle to mix the contents well.
Ｓ ３．２９モルＮａ、 Ｃ
０，０，４５２モル
Ｌｉ２Ｃ０，０，４５２モル
に３ＰＯ４０，１２１モル
ＮＨ４ＰＦ、 ０．０３０モルＬｉ、Ｂ
２Ｏ，０，０６０モル
この後の工程は実施例１〜８の場合と同様にして焼成、
水洗、酸洗処理等を行った。S 3.29 mol Na, C
0,0,452 mol Li2C0,0,452 mol 3PO40,121 mol NH4PF, 0.030 mol Li,B
2O, 0,060 mol The subsequent steps were the same as in Examples 1 to 8, calcination,
Washing with water, pickling, etc. were performed.
得られた螢光体は（Ｌ ８６１ｇｇ Ｐ ｒｇ、 ６１
）ＩＣｅＧｘ、、−４）、 ｏ２Ｓ ： （Ｆ ）の組
成を有するものであり、その平均粒径は３８μｍであっ
た。The obtained phosphor was (L 861gg P rg, 61
) ICeGx, -4), o2S: (F), and its average particle size was 38 μm.
実施例 １０
実施例９におけるＬａ２０．およびＬａＰＯ４の代りに
それぞれＹ、Ｏ，およびｙｐｏ、を用い、他は実施例９
の場合と同様にして螢光体を製造した。Example 10 La20 in Example 9. and Y, O, and ypo were used in place of LaPO4, and the others were Example 9.
A phosphor was produced in the same manner as in the case of .
得られた螢光体は（Ｙ、、 、、、 Ｐｒ、、、。１Ｃ
ａｔｘ１ｏ−６）、 Ｏｘ Ｓ ： （Ｆ ）の組成を
有するものであり、その平均粒径は３６μｍであった。The obtained phosphor is (Y, , , , Pr, , .1C
atx1o-6), OxS: (F), and its average particle size was 36 μm.
実施例 １１
実施例３におけるホウ素化合物Ｌｉ２Ｂ、Ｏ，の量を０
．０１モル（希土類元素１グラム原子に対して０．０２
グラム原子のホウ素を含む）とし、他は実施例１〜８の
場合と同様条件で処理して螢光体を製造した。Example 11 The amount of boron compound Li2B, O, in Example 3 was reduced to 0.
．． 01 mole (0.02 per gram atom of rare earth element)
(containing gram atom boron), and other conditions were the same as in Examples 1 to 8 to produce phosphors.
得られた螢光体は（Ｇｄ、、ｓｓｓ ｐ ｒ、、 ａａ
ｘＣｅ、ｘｌ、−６）２０２Ｓ：（Ｆ）の組成を有する
ものであり、その平均粒径は２５μｍであった。The obtained phosphor is (Gd,, sss pr,, aa
xCe, xl, -6) 202S:(F), and its average particle size was 25 μm.
実施例 １２
実施例３におけるホウ素化合物Ｌｉ、Ｂ、０７の量を０
．２モル（希土類元素１グラム原子に対して０．４ダラ
ム原子のホウ素を含む）とし、他は実施例１〜８の場合
と同様条件で処理して螢光体を製造した。Example 12 The amount of boron compound Li, B, 07 in Example 3 was reduced to 0.
．． 2 mol (contains 0.4 Durham atoms of boron per gram atom of the rare earth element), and otherwise processed under the same conditions as in Examples 1 to 8 to produce phosphors.
得られた螢光体は（Ｇｄ、、 ｓｓｓ Ｐ ｒ、、 ｏ
。、ＣｅＧＸｌ、−６）、 ｏ、 Ｓ ： （Ｆ ）の
組成を有するものであり、その平均粒径は４５μｍであ
った。The obtained phosphor is (Gd,, sss P r,, o
. , CeGXl, -6), o, S: (F), and its average particle size was 45 μm.
実施例 １３
下記材料をビーカーに秤量採取し、これに水を加えて十
分混合した後乾燥する。Example 13 The following materials were weighed into a beaker, water was added thereto, thoroughly mixed, and then dried.
Ｇ ｄ、 ０３０．４１９６モル
Ｌ ａ、 ０ 、 ０．４９９５モル
ＧｄＰ Ｏ４０，１５９８モル
Ｐｒ、Ｏｌ、 ０．０００３３モル
Ｃｅ（ＮＯ３）３ ” ６ Ｈｚ○ ０，００００１
２モル次いで、上記混合物をアクリル製のびんに入れ、
さらに下記材料を加え、びんを回転して内容物を良く混
合させる。G d, 0.4196 mole La, 0, 0.4995 mole GdP O40,1598 mole Pr, Ol, 0.00033 mole Ce(NO3)3'' 6 Hz○ 0,00001
2 mol Then, put the above mixture into an acrylic bottle,
Add the following ingredients and rotate the bottle to mix the contents well.
Ｓ ３．２９モルＮａ、 Ｇ
Ｏ３０，４５２モル
Ｌｉ、 Ｇ Ｏ，０，４５２モ／Ｌ／
に、 Ｐ Ｏ４０，１２１モル
ＮＨ４ＰＦ、 ０．０３０モルＬＬ、
Ｂ４０． ０．０６０モルこの混合材料
をアルミするつぼに詰め、アルミナのふたをした後、空
気中１２５０℃で６時間の焼成を行った。その後の工程
は実施例１〜８の場合と同様の条件で処理して螢光体の
作製を行った。S 3.29 mol Na, G
O30,452 mol Li, GO, 0,452 mo/L/, PO40,121 mol NH4PF, 0.030 mol LL,
B40. 0.060 mol of this mixed material was packed in an aluminum crucible, covered with an alumina lid, and then fired in air at 1250° C. for 6 hours. The subsequent steps were carried out under the same conditions as in Examples 1 to 8 to produce a phosphor.
得られた螢光体は（Ｇｄ０．４に９ＭＧ Ｌａ、、 ４
ｓｓｓＰｒｌ、、、、、ＣｅＢｌｏ−リ、０２Ｓ：（Ｆ
）の組成を有するものであり、その平均粒径は３６μｍ
であった。The obtained phosphor was (Gd0.4 to 9MG La, 4
sssPrl, , , CeBlo-ri, 02S: (F
), and its average particle size is 36 μm.
Met.
実施例 １４
実施例１３におけるＬａ、０，０．４９９５モルの代り
にＹ２Ｏ，０，４９９５モルを用い、他は実施例１３の
場合と同様条件で螢光体を製造した。Example 14 A phosphor was produced under the same conditions as in Example 13 except that 0.4995 mol of Y2O was used in place of 0.4995 mol of La in Example 13.
得られた螢光体は（Ｇｄｏ、ｓｓｓ ｙ、、４ｓｓｓＰ
ｒｏ、 ｏｏ、Ｃｅ、Ｘｉ、−６）２ｏ２Ｓ ： （
Ｆ ）の組成を有するものであり、その平均粒径は３５
μｍであった。The obtained phosphor was (Gdo, sss y, 4sssP
ro, oo, Ce, Xi, -6)2o2S: (
F), and its average particle size is 35
It was μm.
上記の諸実施例においては材料成分の一つとしてフッ素
化合物ＮＨ４ＰＦ、を用いた場合について説明してきた
が、この代りにＫＣＱ等の塩素化合物を用いても同様の
結果が得られている。In the above examples, the case where the fluorine compound NH4PF is used as one of the material components has been described, but similar results have been obtained when a chlorine compound such as KCQ is used instead.
また、ホウ素化合物の混合形態として上記諸実施例にお
イテはＨ２ＢＯ３、Ｂ、Ｏ，、Ｌｉ、Ｂ４Ｏ７、Ｋ、Ｂ
４０．、に、Ｂ、０４．ＮａＢＯ２およびＬｉＢ Ｏ。In addition, as the mixed form of the boron compound, H2BO3, B, O,, Li, B4O7, K, B
40. , to, B, 04. NaBO2 and LiBO.
の中から選ばれる少なくとも１種の化合物を用いた場合
について説明したが、混合形態としてはこれに限定する
ものではなく、例えばＬｉ、Ｂ、Ｏ□の代りにＬｉ、Ｇ
ｏ、とＢ２Ｏ３との混合物。Although the case where at least one compound selected from among these is used has been described, the mixed form is not limited to this. For example, Li, G instead of Li, B, and O□ are used.
o, and a mixture of B2O3.
Ｎａ、Ｂ４０．の代りにＮａ、Ｇｏ、とＢ２０．との混
合物など反応によって容易に上記化合物を生ずるような
原材料を用いても同様の結果が得られることは言うまで
もない。Na, B40. Instead of Na, Go, and B20. It goes without saying that similar results can be obtained by using raw materials that easily produce the above-mentioned compounds by reaction, such as mixtures with .
以上述べてきたように、シンチレータ用希土類オキシサ
ルファイドセラミックス製造用材料としての希土類オキ
シサルファイド螢光体の製造において、本発明の製造方
法、特に焼成材料成分の一つとしてホウ素化合物を希土
類元素１グラム原子当り０．０２〜０．４グラム原子の
範囲の量で用いること、によって、従来技術の有してい
た課題を解決して、平均粒径の大きな希土類オキシサル
ファイド螢光体を得ることができた。As described above, in the production of a rare earth oxysulfide phosphor as a material for producing rare earth oxysulfide ceramics for scintillators, the production method of the present invention is used, particularly when a boron compound is added as one of the components of the fired material to 1 gram atom of the rare earth element. By using an amount in the range of 0.02 to 0.4 gram atom per gram atom, it was possible to solve the problems of the prior art and obtain a rare earth oxysulfide phosphor with a large average particle size. .
また、この螢光体を用いて熱間静水圧加圧法でセラミッ
クシンチレータを作製することによって、極めて発光効
率の高いＸ１ｉＣＴ用検出器を得ることができた。In addition, by producing a ceramic scintillator using this phosphor by hot isostatic pressing, it was possible to obtain a detector for X1iCT with extremely high luminous efficiency.
Claims (2)
（Ｆ）の成分からなる混合物を加熱焼成する工程と、次
いで、該焼成物を冷却後水洗する工程とからなることを
特徴とする螢光体の製造方法。 （Ａ） 一般式（Ｌｎ＿１＿−＿ｘ Ｍ＿ｘ）＿２Ｏ＿
３で表わされる酸化物。但し、ＬｎはＹ、Ｌａ、Ｇｄの
中から選ばれる少なくとも１種の元素、ＭはＰｒ、Ｅｕ
、Ｔｂの中から選ばれる少なくとも１種の元素、ｘは０
．００００３〜０．１の範囲の値。 （Ｂ） 元素ＬｎおよびＭのリン酸塩化合物。量はＬｎ
とＭとの総原子数の３〜３０原子パーセントの範囲。 （Ｃ） 加熱分解によってＣｅ＿２Ｏ＿３を生ずるＣｅ
化合物。 （Ｄ） 加熱により硫化アルカリおよびポリ硫化アルカ
リを生ずる組成物。 （Ｅ） ホウ素化合物。 （Ｆ） フッ素化合物あるいは塩素化合物。1. The following (A), (B), (C), (D), (E),
A method for producing a phosphor, comprising the steps of heating and baking a mixture consisting of the components (F), and then washing the baked product with water after cooling. (A) General formula (Ln_1_-_x M_x)_2O_
Oxide represented by 3. However, Ln is at least one element selected from Y, La, and Gd, and M is Pr and Eu.
, at least one element selected from Tb, x is 0
．． Values in the range 00003 to 0.1. (B) Phosphate compounds of elements Ln and M. The amount is Ln
and M in the range of 3 to 30 atomic percent of the total number of atoms. (C) Ce that produces Ce_2O_3 by thermal decomposition
Compound. (D) A composition that produces alkali sulfide and alkali polysulfide upon heating. (E) Boron compound. (F) Fluorine compounds or chlorine compounds.
３、Ｌｉ＿２Ｂ＿４Ｏ＿７、Ｎａ＿８Ｂ＿４Ｏ＿７、Ｋ
＿２Ｂ＿４Ｏ＿７、Ｋ＿２Ｂ＿２Ｏ＿４、ＮａＢＯ＿２
およびＬｉＢＯ＿２の中から選ばれる少なくとも１種の
ホウ素化合物であることを特徴とする特許請求の範囲第
１項記載の螢光体の製造方法。2. The above boron compounds are H_3BO_3, B_2O_
3, Li_2B_4O_7, Na_8B_4O_7, K
_2B_4O_7, K_2B_2O_4, NaBO_2
2. The method for producing a phosphor according to claim 1, wherein the phosphor is at least one boron compound selected from LiBO_2 and LiBO_2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15489788A JP2625000B2 (en) | 1988-06-24 | 1988-06-24 | Phosphor manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15489788A JP2625000B2 (en) | 1988-06-24 | 1988-06-24 | Phosphor manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH026590A true JPH026590A (en) | 1990-01-10 |
| JP2625000B2 JP2625000B2 (en) | 1997-06-25 |
Family
ID=15594349
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15489788A Expired - Fee Related JP2625000B2 (en) | 1988-06-24 | 1988-06-24 | Phosphor manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2625000B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000178554A (en) * | 1998-10-28 | 2000-06-27 | General Electric Co <Ge> | Rare earth x-ray scintillator composition |
| JP2004238583A (en) * | 2003-02-10 | 2004-08-26 | Toshiba Corp | Scintillator and radiation testing apparatus using the same |
| US7230248B2 (en) * | 2003-09-24 | 2007-06-12 | Kabushiki Kaisha Toshiba | Ceramic scintillator, and radiation detector and radiographic examination apparatus using same |
| EP1816241A1 (en) * | 2004-11-08 | 2007-08-08 | Tohoku University | Pr-CONTAINING SINGLE CRYSTAL FOR SCINTILLATOR, PROCESS FOR PRODUCING THE SAME, RADIATION DETECTOR AND INSPECTION APPARATUS |
-
1988
- 1988-06-24 JP JP15489788A patent/JP2625000B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000178554A (en) * | 1998-10-28 | 2000-06-27 | General Electric Co <Ge> | Rare earth x-ray scintillator composition |
| JP2004238583A (en) * | 2003-02-10 | 2004-08-26 | Toshiba Corp | Scintillator and radiation testing apparatus using the same |
| US7230248B2 (en) * | 2003-09-24 | 2007-06-12 | Kabushiki Kaisha Toshiba | Ceramic scintillator, and radiation detector and radiographic examination apparatus using same |
| EP1816241A1 (en) * | 2004-11-08 | 2007-08-08 | Tohoku University | Pr-CONTAINING SINGLE CRYSTAL FOR SCINTILLATOR, PROCESS FOR PRODUCING THE SAME, RADIATION DETECTOR AND INSPECTION APPARATUS |
| JPWO2006049284A1 (en) * | 2004-11-08 | 2008-08-07 | 株式会社 東北テクノアーチ | Single crystal for scintillator containing Pr, manufacturing method thereof, radiation detector and inspection apparatus |
| EP1816241A4 (en) * | 2004-11-08 | 2010-04-28 | Tohoku Techno Arch Co Ltd | Pr-CONTAINING SINGLE CRYSTAL FOR SCINTILLATOR, PROCESS FOR PRODUCING THE SAME, RADIATION DETECTOR AND INSPECTION APPARATUS |
| CN102888652A (en) * | 2004-11-08 | 2013-01-23 | 东北泰克诺亚奇股份有限公司 | Pr-containing single crystal for scintillator, process for producing the same, radiation detector and inspection apparatus |
| JP5389328B2 (en) * | 2004-11-08 | 2014-01-15 | 株式会社 東北テクノアーチ | Single crystal for scintillator containing Pr, its manufacturing method, radiation detector and inspection apparatus |
| US9834858B2 (en) | 2004-11-08 | 2017-12-05 | Tohoku Techno Arch Co., Ltd. | Pr-containing scintillator single crystal, method of manufacturing the same, radiation detector, and inspection apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2625000B2 (en) | 1997-06-25 |
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